Process of halogenizing organic fluids.



No. 721,961. I PATENTED MAR. 3, 1903.

L. MARGKWALD.

I ROGESS 0F HALOGENIZING ORGANIC FLUIDS.

APPLICATION FILED AUG. 21, 1902. N0 MODEL.

Eyz.

U ITED STATES PATENT OFFICE.

LEO MARCKVVALD, OF CHARLOTTENBURG, GERMANY.

PROCESS OF HALOGENIZING ORGANIC FLUIDS.

SPECIFICATION forming part of Letterelatent No. 721,961, dated March 3,I903.

Application filed August 21, 1902} Serial No. 120.502. (No specimens.)

To all whom' it may concern:

Be it known that I, LEO VMARCKWALD, doctor ofphilosophy, a subject ofthe King of Prussia, German Emperor, residing at 35 Weimarerstrasse,Charlottenburg, Kingdom of Prussia, German Empire, have invented new anduseful Improvements in Processes of Halogenizing Organic FluidSubstances, of which the following is a specification.

The invention relates to the manufacture of organic halogen com poundsfrom fluid rganic substances.

Hitherto it has been impossible to avoid in the production of organichalogen compounds that a larger amount than desired of halogen atomswould enter into the molecule of the substance to be treated. If oneintended, for instance, to produce from toluol (C H CH by the action ofchlori'n benzylchlorid, (O H OH Cl), benzalchlorid (C H OHOl andbenzotrichlorid (C H CGI were formed by the first action of the chlorinon toluol,where, as in the production of benzalchlorid (O H CHOI frombonzylohlorid, (O H OH O1) also benzotrichlorid (C H GOI was formed fromthe beginning of the process. The said higher chlorinated by-produOtsrendered the manufacture-of the halogen compound that one wished toobtain in a pure state difficult. The object of this invention is toavoid the above-stated difficulties and to enable the introduction of acertain number of halogen atoms into fluid organic substances, wherebythe organic halogen compounds may .be obtained free from higherchlorinated organic compounds.

This process consists in that I cause during the halogenizing processconstantly fresh raw material to be exposed to the action of the halogenand that the halogen compound formed in a small quantityis withd rawusimultaneously with the unattacked raw material from the further actionof the halogen. Inmy process, therefore, the unattached raw material isin a large surplus with reference to the amount of halogen. The rawmaterial is only a short time exposed to the action of the halogen.Therefore only a small proportion of the raw material is converted intothe halogen compound. From the mixture of raw material and halogencompound resultin g in the process I separate the raw material,

which is subjected again to the action of the.

halogen and the halogen compound, which I may purify when desired.

I may carry out my process inusing an apparatus illustrated in theaccompanyingdrawings, in which-- Figure 1 is a viewpartly in verticalsection; Fig. 2, a view of a modification of my apparatus.

Similar letters refer to similar parts throughout both views.

a is a still of suitable construction.

I) is the rectification -column, preferably composed of several chamberscommunicating with each other by overflow-tubes placed on the top of thestill a; c, the vessel, of suitable form, in which the action of thehalogen on the organic compound to be treated is carried out, whichvessel -I shall designate as halogenizing vessel.

01 is a reflux-condenser. c is the tube leading the halogen into thevessel 0.

f is a reflux-tube. g is the condensing apparatus. h is the tube leadingthe material to be treated into the apparatus.

'i is the overflow-tube.

k is the tube carrying away the hydrohalogen acid formed in the process.I describe the manner in which I carry out my process in describing theproduction of benzylchlorid (O H OH Ol) from toluol,.((L H CH I place inthe still aasuitable amount of toluolsay fifty kilosand a suitableamount of a halogenizing agentsay 0.5 kilos phosphorus trichlorid(POM-and heat in suitable manner the mixture, so that the vapors of-thesaid substance enter through the column b and the condensing apparatusginto the Vessel c, in which the action of the halogen on the toluol (01L01 to be treated is to be carried out, and from the said vessel 0 intothe reflux-cooler d, in which latter a condensation of the vapor isefiected. The toluol returning fills the vessel 0 by being maintained toboiling temperature by the toluol-vapors. If the level ofthe toluolattains the refluxt'ube f, the toluol returns by the said tube f intothe still up. Now I introduce by the tube 6 chlorin into the liquoruntil a thermometer placed in the condensing apparatusfg shows i atemperature above the boiling-point of to- 1uol-i. 6., 111centigrade-and indicates the chlorination of the toluol to be treatedhas been finished, so that in the still a exclusively or nearlyexclusively the chlorination product is present. Now I introduce by thetube 70 an amount of tolu'ol equivalent to the amount of chlorinintroduced in the same time into the apparatus. The toluol introduced ismixed with the toluol present in the vessel and refluxes with the latterquoted amount of toluol,-so that as the tolnol continuously is vaporizedthe still a is filled with benzylchlorid that flows away by the tube 2'.The product so obtained may be purified bya rectifying process-forinstance, by fractional distillation. In the described apparatus allorganic-fluid substances that are to be halogenized at boilingtemperature may be treated. One may produce in the described apparatusbenzalchlorid-(C H CHOl from benzylchlorid, chlorin acetic acid v(CHOLCOOH) from acetic acid, (CILOOOIL) chlorin malonic acid, OI-ICl(CO H)or bromin malonic acid, CHBr(C0 l-l) from malonic acid, CH, (CO H) insubstituting benzylchlorid, acetic acid, malonic acid for toluol, orbromin for chlorin in the described example. I may also introduce thefluid from the halogenizing vessel 0 into a chamber of the column binstead of introducing it into the still a. By this modification Iobtain the efiect that the condensing apparatus may work less, wherebyfuel is ecouomized.

If I intend to carry out the halogenizing process instead of at theboiling temperature of the substance to be treated, as described, at alower temperature, as would be required for the manufactu reofchlorinbenzol (C H Cl) from beuzol, (O H J I use the apparatusillustrated in Fig. 2 of the accompanying drawings. I introduce thecondensed vapors instead of the vapors'into the halogenizing vessel c.For effecting this I interpose between the condensing apparatus 9 andthe halogenizing vessel 0 a cooler d and lead the vapors coming from thecondensing apparatus 9 through the cooler d before they enter the vessel0. Besides the quoted modification the process is carried out in amanner analogous to the described production of bony]- chlorid fromtoluol.

Instead of one vessel for carrying out the action of the halogen on theorganic substance I may also use several vessels that are incommunication with one still, from which they are charged in the sametime or intermittently.

What I claim as my invention, and desire to secure by Letters Patent,is-- 1. Process for halogeniz-ing organic fluid substances, especiallyfor introducing a certain number of halogen atoms into the molecule ofthe said substances, consisting in that a certain portion of thesubstances is treated with halogen, new portions of the substances to betreated are continuously subjected to the action of halogen, and themixture so obtained of unattacked substances and halogenized substancesis continuously Withdrawn from the further action of the halogen, sothat during the halogenizing process the proportion of the unattackedsubstances is very large with reference to the halogen.

2. Process for halogenizing organic fluid substances, especially forintroducing a certain number of halogen atoms into the molecules of thesaid substances, consisting in that a certain portion of the substancesis treated with halogen, new portions of the substances to be treatedare continuously subjected to the action of halogen, the mixture soobtained of unattacked substances and halogenized substances iscontinuously withdrawn from the further action of the halogen, thehalogenized substances are separated from the mixture and theunhalogenized substances are subjected continuously to the action ofhalogen.

In testimony whereof I have signed my name to this specification in thepresence of two subscribing witnesses.

LEO MAROKWALD.

Witnesses:

HENRY HASPER, WILLIAM MAYNER.

